CN1146630C - Flame resistant polycarbonate/ABS plastic molding materials - Google Patents

Flame resistant polycarbonate/ABS plastic molding materials Download PDF

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CN1146630C
CN1146630C CNB998079316A CN99807931A CN1146630C CN 1146630 C CN1146630 C CN 1146630C CN B998079316 A CNB998079316 A CN B998079316A CN 99807931 A CN99807931 A CN 99807931A CN 1146630 C CN1146630 C CN 1146630C
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moulding compound
component
weight part
compound
oxide
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CN1307611A (en
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T·埃克尔
M·佐贝尔
D·维特曼
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Covestro Deutschland AG
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K7/00—Use of ingredients characterised by shape
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
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Abstract

The invention relates to polycarbonate/ABS plastic molding materials containing phosphazenes and inorganic nanoparticles which exhibit an excellent flame protection and very good mechanical properties.

Description

Flame-resistant polycarbonate/ABS moulding compound
Technical field
The present invention relates to a kind of polycarbonate/ABS moulding compound that excellence is anti-flaming and splendid mechanical property, comprise phosphonitrile and inorganic nanoparticles that shows.
Background technology
DE-A 196 16 968 has described a kind of polymerizable phosphazene derivative, its production method and has been used for the application of varnish, coating, filler, flush coat composition, tackiness agent, mo(u)lded item or film aspect as curable base-material.
WO 97,/40 092 has described a kind of anti-flaming moulding compound, by thermoplastic polymer and unsubstituted phosphonitrile (PN N-xH 1-yType) makes.
EP-A 728 811 has described a kind of thermoplastic blend, is made up of aromatic polycarbonate, graft copolymer, multipolymer and phosphonitrile, shows good anti-flaming performance, shock strength and heat-resisting.
No matter WO 97/,400 92 or EP-A 728 811 all do not describe the combination of phosphonitrile and inorganic nanoparticles.
Summary of the invention
The purpose of this invention is to provide a kind of polycarbonate/ABS moulding compound, it has excellent anti-flaming, high heat-resisting and splendid mechanical property, as notched Izod impact strength, weld line strength and proof stress be full of cracks.This kind over-all properties is data processing purposes special requirement, for example makes the shell of indicating meter, printer, duplicating machine and so on usefulness.
Have now found that the PC/ABS moulding compound when comprising the combination of phosphonitrile and inorganic nanoparticles, will show desirable performance.
Therefore, the invention provides a kind of thermoplastic composition, comprise the inorganic powder that polycarbonate and/or polyestercarbonate, graftomer, phosphonitrile and average particulate diameter are less than or equal to 200nm, said composition also can comprise other polymkeric substance for example thermoplastic ethylene's base (being total to) polymkeric substance and/or poly terephthalic acid alkane diol ester and, randomly, other additives.
The present invention preferably provides a kind of thermoplastic composition, comprises:
A) 40～99, preferred 60～98.5 weight part aromatic polycarbonate and/or polyestercarbonates
B) 0.5～60, preferred 1～40, the graftomer of the following component of 2～25 weight parts especially:
B.1) 5～95, preferred 30～80wt%1 kind or multiple vinyl monomer are grafted to
B.2) 95～5, on preferred 20～70wt%1 kind or the multiple grafting main chain, the second-order transition temperature of this main chain is less than 10 ℃, preferably less than 0 ℃, and especially preferably less than-20 ℃,
C) 0～45, preferred 0～30, at least a kind of thermoplastic polymer of especially preferred 2～25 weight parts is selected from thermoplastic ethylene's base (being total to) polymkeric substance and poly terephthalic acid alkane diol ester,
D) 0.1～50, preferred 2～35, at least a kind of component that is selected from following general formula phosphonitrile of 5～25 weight parts especially
Figure C9980793100061
Wherein
Every kind of situation of R can be identical or different, represents amino, and is optional by halogenation, preferably by the halogenated C of fluorine under every kind of situation 1～C 8Alkyl or C 1～C 8Alkoxyl group, under every kind of situation randomly by alkyl, preferred C 1～C 4The C that alkyl and/or halogen, preferred chlorine and/or bromine replace 5～C 6Cycloalkyl, C 6～C 20Aryl, preferred phenoxy group, naphthyloxy, perhaps C 7～C 12Aralkyl, preferred phenyl-C 1～C 4-alkyl.
K represents 0 or 1～15 number, preferred 1～10 number,
E) 0.5～40 weight part, preferred 1～25, especially preferred 2～15 weight part average particulate diameters are less than or equal to the fine dispersion inorganic powder of 200nm, and
F) 0～5, preferred 0.15～1, especially preferred 0.1～0.5 weight part fluorinated polyolefin.
Component A
Being fit to component A aromatic polycarbonate of the present invention and/or aromatic polyestercarbonates is known in the literature, perhaps can adopt by the preparation of the known method of document (about the preparation of aromatic polycarbonate can referring to, Schnell for example, " polycarbonate chemistry and physics ", international scientific press, 1964, and DE-AS 1 495 626, DE-OS 2 232 877, DE-OS 2 703 376, DE-OS 2 714 544, DE-OS 3 000 610, DE-OS 3 832 396; About the preparation of aromatic polyestercarbonates, for example referring to DE-OS 3 077 934).
The preparation example of aromatic polycarbonate is as can be by diphenol and carbonyl halide, preferred phosgene, and/or with aromatic dicarboxylic acid two carboxylic acid halides, two carboxylic acid halides of preferred benzene dicarboxylic acid according to the phase interface method, randomly adopt chain terminator, monohydric phenol for example, and randomly adopt trifunctional or the above branching agent of trifunctional, for example triphenol or four phenol are implemented.
The diphenol that is used to prepare aromatic polycarbonate and/or aromatic polyestercarbonates is those of general formula (I) preferably:
Wherein
A represents singly-bound, C 1～C 5Alkylidene group, C 2～C 5(1,1-) alkylidene group, C 5～C 6The ring (1,1-) alkylidene group ,-O-,-SO-,-CO-,-S-,-SO 2-, C 6～C 12Arylidene also can further condense the optional heteroatomic aromatic ring that comprises on it,
Perhaps general formula (II) or residue (III)
Every kind of situation of B is represented C 1～C 12Alkyl, preferable methyl, halogen, preferred chlorine and/or bromine
Every kind of situation of x represents 0,1 or 2 independently of one another,
P represents 1 or 0, and
R 5And R 6, with regard to each X 1Can be independently of one another, select individually, represent hydrogen or C 1～C 6Alkyl, preferred hydrogen, methyl or ethyl,
X 1Represent carbon, and
M represents 4～7 integer, and preferred 4 or 5, condition is R 5With R 6At at least 1 atom X 1On be alkyl simultaneously.
Preferred diphenol is quinhydrones, Resorcinol, dihydroxybiphenyl phenol, two (hydroxyphenyl)-C 1～C 5-alkane, two (hydroxyphenyl)-C 5～C 6-cycloalkanes, two (hydroxyphenyl) ether, two (hydroxyphenyl) sulfoxide, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfone and α, the derivative of α-two (hydroxyphenyl) diisopropyl benzene and ring brominated and/or ring chlorinated.
Particularly preferred diphenol is 4,4 '-dihydroxybiphenyl, dihydroxyphenyl propane, 2, two (4-the hydroxyphenyl)-2-methylbutanes, 1 of 4-, two (4-hydroxyphenyl) hexanaphthenes, 1 of 1-, two (the 4-hydroxyphenyl)-3,3 of 1-, 5-trimethyl-cyclohexane, 4,4 '-dihydroxyl diphenyl sulfide, 4,4 '-dihydroxy diphenylsulphone and two-and tetrabormated or chlorinated derivatives, for example 2, two (the 3-chloro-4-hydroxyphenyl) propane, 2 of 2-, two (3, the 5-two chloro-4-hydroxyphenyl) propane or 2 of 2-, two (3, the 5-two bromo-4-hydroxyphenyl) propane of 2-.
2, two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-are especially preferred.
Diphenol can use individually or with the form of mixtures of any hope.
This diphenol is known or can adopt in the document known method to produce in the document.
The chain terminator that is fit to the preparation thermoplastic aromatic polycarbonate for example is phenol, P-Chlorophenol, p-tert-butylphenol or bromol, and long chain alkylphenol, for example according to DE-OS 2 842005 disclosed 4-(1, the 3-tetramethyl butyl)-phenol; Or always have the monoalkyl phenol or the dialkyl phenol of 8～20 carbon atoms in the alkyl substituent, for example, 3,5-di-tert-butylphenol, to isooctylphenol, to uncle's octyl phenol, to 4-dodecylphenol and 2-(3,5-dimethyl heptyl) phenol and 4-(3,5-dimethyl heptyl) phenol.The consumption of chain terminator, the diphenol total mole number that uses with every kind of situation as benchmark generally between 0.5mol%～10mol%.
Thermoplastic aromatic polycarbonate's weight-average molecular weight (M w, for example by super centrifugal or determination of light scattering) and between 10000～200000, preferred 20000～80000.
The thermoplastic aromatic polycarbonate can realize branching according to known way, especially preferably adds up to benchmark 0.05～2.0mol% trifunctional or the compound more than the trifunctional by adding with the diphenol that uses, and for example has 3 or more than those of 3 phenolic group groups.
Homo-polycarbonate and Copolycarbonate all are suitable for.Also can use 1～25wt% in the preparation of component A Copolycarbonate of the present invention, preferred 2.5～25wt% (with respect to the total consumption of diphenol) has the polydiorganosiloxane of bis (hydroxy-aromatic) oxygen end group.They be known (for example referring to United States Patent (USP) 3,419 634) or can adopt known method preparation in the document.The preparation example of Copolycarbonate that contains polydiorganosiloxane is as being described among the DE-OS 3 334 782.
Except the dihydroxyphenyl propane homo-polycarbonate, preferred polycarbonate also has dihydroxyphenyl propane and the highest 15mol%, for the diphenol total mole number, other are as preferred or especially preferred diphenol, particularly with 2, the Copolycarbonate that two (3, the 5-two bromo-4-hydroxyphenyl) propane of 2-generate.
Aromatic dicarboxylic acid two carboxylic acid halides that are used to prepare aromatic polyestercarbonates are m-phthalic acid, terephthalic acid, phenyl ether 4 preferably, 4 '-dicarboxylic acid and 2, the diacid chloride of 6-naphthalene dicarboxylic acids etc.
M-phthalic acid and diacid chloride terephthalic acid are especially preferred in the mixture of 1: 20～20: 1 ratios.
Also use carbonyl halide in addition, preferred phosgene is as two functional acid derivatives in the polyestercarbonate preparation.
Except monohydric phenol above-mentioned, the chain terminator that also can consider to be used to prepare aromatic polyestercarbonates comprises its chlorinated carbonates and aromatic monocarboxylate's acyl chlorides, and it can be randomly by C 1～C 22Alkyl group or halogen atom replace, and also comprise aliphatic C 2～C 22The acyl chlorides of monocarboxylic acid.
The consumption of chain terminator is 0.1～10mol% under every kind of situation, is benchmark with the diphenol mole number under the situation of phenols chain terminator wherein, and next in the situation of monocarboxylic acid acyl chlorides chain terminator be benchmark with dicarboxylic acid diacid chloride mole number.
Aromatic polyestercarbonates also can comprise the aromatic hydroxycarboxylic acids of blending.
Aromatic polyestercarbonates can be a line style or by (also can be referring to the DE-OS 2 940 024 and the DE-OS 3 007 934 about this point) of currently known methods branching.
Spendable branching agent for example is three-or the polyfunctional carboxylic acids acyl chlorides, for example 1,3,5-benzenetricarboxylic acid three acyl chlorides, cyanuric acid three acyl chlorides, 3,3 '-, 4,4 '-benzophenone tetracarboxylic acid, four acyl chlorides, 1,4,5,8-naphthalene tetracarboxylic acid four acyl chlorides or 1,2,4,5-pyromellitic acid four acyl ammonia, its consumption is between 0.01～1.0mol% (for dicarboxylic acid diacid chloride consumption), perhaps three-or multifunctional phenol, for example Phloroglucinol, 4,6-dimethyl-2,4,6-three (4-hydroxyphenyl)-2-heptene, 4,4-dimethyl-2,4,6-three (4-hydroxyphenyl) heptane, 1,3,5-three (4-hydroxyphenyl) benzene, 1,1,1-three (4-hydroxyphenyl) ethane, three (4-hydroxyphenyl) phenylmethane, 2,2-two [4, two (4-hydroxyphenyl) cyclohexyl of 4-] propane, 2, two (the 4-hydroxyphenyl sec.-propyl) phenol of 4-, four (4-hydroxyphenyl) methane, 2, two (2-hydroxy-5-methyl base the benzyl)-4-methylphenols of 6-, 2-(4-hydroxyphenyl)-2-(2, the 4-dihydroxy phenyl) propane, four (4-[4-hydroxyphenyl sec.-propyl] phenoxy group) methane, 1,4-pair [4,4 '-dihydroxyl triphenyl) methyl] benzene, its consumption is benchmark between 0.01-1.0mol% with the diphenol consumption.The phenols branching agent can be introduced in company with diphenol when beginning together; The acyl chlorides branching agent can be introduced together in company with diacid chloride.
The ratio of carbonate structural unit in the Celanex carbonic ether can change arbitrarily.The ratio of carbonate group is the highest 100mol% preferably, especially the highest 80mol%, and especially preferably the highest 50mol% is a benchmark with ester group and carbonate group summation.The ester of aromatic polyestercarbonates and carbonate moiety all can block form exist, and perhaps randomly are distributed in this polycondensation product.
Relative solution viscosity (the η of aromatic polycarbonate and polyestercarbonate Rel) between 1.18～1.4, preferred 1.22～1.3 (0.5g polycarbonate or the polyestercarbonate solution in the 100mL methylene dichloride is 25 ℃ of mensuration).
Thermoplastic aromatic polycarbonate and polyestercarbonate can use separately or with the thing form that is mixed with each other of any hope.
B component
B component comprises a kind or multiple graft copolymer, is made of following:
B.1) 5～95, preferred 30～80wt%1 kind or multiple vinyl monomer are grafted to
B.2) 95～5, on preferred 70～20wt%1 kind or the multiple grafting main chain, the second-order transition temperature of this main chain is less than 10 ℃, preferably less than 0 ℃, especially preferably less than-20 ℃.
Grafting main chain mean particle size (d B.2 50Value) usually between 0.05～5 μ m, preferred 0.10～0.5 μ m, especially preferred 0.20～0.40 μ m.
Monomers B .1 is the mixture of following component preferably:
B.1.1 50～99 parts by weight of ethylene base aromatic hydrocarbons and/or nuclear substituted vinyl-arene (for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, to chloro-styrene) and/or methacrylic acid (C 1～C 8)-alkyl ester (for example methyl methacrylate, Jia Jibingxisuanyizhi), and
B.1.2 1～50 parts by weight of ethylene base prussiate (unsaturated nitrile, for example vinyl cyanide and methacrylonitrile) and/or (methyl) vinylformic acid (C 1～C 8)-alkyl ester (for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and/or olefinically unsaturated carboxylic acid derivatives (for example acid anhydrides and imide) (for example maleic anhydride and N-phenylmaleimide).
Preferred monomers B .1.1 is selected from least a kind in monomer styrene, alpha-methyl styrene and the methyl methacrylate; Preferred monomers B .1.2 is selected from least a kind in monomer vinyl cyanide, maleic anhydride and the methyl methacrylate.
Especially preferred monomer is B.1.1 vinylbenzene and B.1.2 vinyl cyanide.
B.2, the grafting main chain that preferably is used for graftomer B is an elastoprene for example, EP (D) M rubber, that is, and based on the ethylene/propene and the rubber of diene randomly, rubber such as acrylate, urethane, siloxanes, chloroprene and ethylene/vinyl acetate.
Preferred grafting main chain B.2 be the mixture of the elastoprene rubber of divinyl, isoprene etc. (for example based on) or elastoprene or elastoprene or its mixture and other copolymerisable monomers (for example, meet B.1.1 and B.1.2 those) multipolymer, condition is: the second-order transition temperature of B component .2 is less than 10 ℃, preferably less than 0 ℃, especially preferably less than-10 ℃.
Pure polybutadiene rubber is especially preferred.
Especially preferred polymer B for example is abs polymer (emulsion, body and suspension ABS), for example be described among DE-OS 2 035 390 (=US-PS 3 644 574) or the DE-OS 2 248242 (=GB-PS 1 409 275), perhaps Ulmann shows " the technology chemistry is complete works of ", volume 19 (1980), pp.280 rises.Grafting main chain gel content B.2 is 30wt% at least, preferably 40wt% (measuring in toluene) at least.
Graft copolymer B system adopts the radical polymerization preparation, for example adopts emulsion, suspension, solution or mass polymerization, preferably adopts letex polymerization.
Specially suitable graft rubber is that according to US-P 4 937 285, employing comprises the abs polymer of the initiator system of organic hydroperoxide and xitix by the redox initiation preparation.
As everyone knows, not necessarily all be grafted to during the graft reaction on the grafting main chain, therefore in view of grafted monomer, graftomer B, also be interpreted as according to the present invention, comprise that those grafted monomer (are total to) polymerization and obtain in the presence of the grafting main chain, again product through during post-treatment, separating.
Suitable polymers B acrylic elastomer is B.2 preferably by alkyl acrylate, randomly with the highest other polymerizables of 40wt% B.2, the polymkeric substance of ethylene linkage unsaturated monomer preparation of being equivalent to.Preferred polymerizable acrylic ester comprises C 1～C 8Alkyl ester, for example ester of methyl, ethyl, butyl, n-octyl and 2-ethylhexyl; The haloalkyl ester, preferred halo C 1～C 8-alkyl ester, for example vinylformic acid chloro ethyl ester and these monomeric mixtures.
The monomer that has more than 1 polymerizable double bond also can participate in polymerization, so that produce crosslinked.Crosslinked (effect) monomeric preferred example be 3～8 carbon atom unsaturated monocarboxylics and 3～12 carbon atoms unsaturated single hydroxyl alcohol or 2～20 carbon atoms, the ester of the saturated polyol of 2～4 hydroxyls is arranged, for example Ethylene glycol dimethacrylate, allyl methacrylate; Many unsaturated heterocyclic compounds, for example cyanurate of trivinyl and triallyl; The polyfunctional vinyl compound, for example two-and trivinylbenzene; And tricresyl phosphate allyl ester and diallyl phthalate.
Preferred cross-linking monomer is allyl methacrylate, Ethylene glycol dimethacrylate, diallyl phthalate and the heterogeneous ring compound with at least 3 ethylene linkage unsaturated groups.
Especially preferred cross-linking monomer is cyclic monomer cyanuric acid triallyl ester, tricarbimide triallyl ester, three acryloyls, six hydrogen-s-triazine, triallyl benzene.The consumption of cross-linking monomer is preferably between 0.02～5, and especially B.2 0.05～2wt% is benchmark with the grafting main chain.
Advantageously, will have the ring-type cross-linking monomer quantity limitation of at least 3 ethylene linkage unsaturated groups in the level that is lower than grafting main chain 1wt% B.2.
Except that acrylate, can choose wantonly be used to prepare the grafting main chain B.2 " other " preferred polymerizable ethylene linkage unsaturated monomer of diene for example be vinyl cyanide, vinylbenzene, alpha-methyl styrene, acrylamide, vinyl C 1-C 6-alkyl oxide, methyl methacrylate, divinyl.Be the emulsion polymer that gel content is at least 60wt% preferably as grafting main chain acrylic elastomer B.2.
B.2, another kind of suitable grafting main chain is the silicon rubber with active cross-linking part, for example is described among DE-OS 3 704 657, DE-OS 3 704 655, DE-OS 3 631 540 and the DE-OS3 631 539.
Grafting main chain gel content is B.2 measured (M.Hoffmann, H.Kr  mer, R.Kuhn, " polymer analysis " volume I and II, Georg Thieme press, Stuttgart 1977) in appropriate solvent.
Mean particle size d 50Be a kind of like this particle diameter, less than respectively accounting for 50wt% with particle greater than this diameter.This numerical value can adopt ultracentrifuge method to measure (W.Scholtan, H.Lange, " colloid and polymkeric substance magazine " 250 (1972), 782～1796).
Component C
Component C comprise a kind or multiple thermoplastic ethylene's base (being total to) polymkeric substance C.1 and/or the poly terephthalic acid alkane diol ester C.2.
C.1, suitable vinyl (being total to) polymkeric substance is at least a kind of following polymer of monomers: vinyl-arene, vinyl cyanide (unsaturated nitrile), (methyl) vinylformic acid (C 1～C 8The derivative of)-alkyl ester, unsaturated carboxylic acid and unsaturated carboxylic acid (for example acid anhydrides and imide).Especially suitable (being total to) polymkeric substance is by those of following monomer preparation:
C.1.1 50～99, preferred 60～80 parts by weight of ethylene base aromatic hydrocarbons and/or nuclear substituted vinyl-arene (for example vinylbenzene, alpha-methyl styrene, p-methylstyrene, to chloro-styrene) and/or methacrylic acid (C 1～C 8)-alkyl ester (for example methyl methacrylate, Jia Jibingxisuanyizhi) and
C.1.2 1～50, preferred 20～40 parts by weight of ethylene base prussiates (unsaturated nitrile), for example vinyl cyanide and methacrylonitrile, and/or (methyl) vinylformic acid (C 1～C 8The derivative (for example acid anhydrides and imide) (for example maleic anhydride and N-phenylmaleimide) of)-alkyl ester (for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and/or unsaturated carboxylic acid (for example toxilic acid) and/or unsaturated carboxylic acid.
C.1, (being total to) polymkeric substance is resinoid, thermoplastic and does not contain rubber.
C.1.1 vinylbenzene is especially preferred with the multipolymer of vinyl cyanide C.1.2.
C.1, (being total to) polymkeric substance is known, can be by radical polymerization, and particularly emulsion, suspension, solution or mass polymerization prepare.C.1, this component (is total to) the molecular weight M of polymkeric substance w(weight average is measured by scattering of light or settling process) is between 15000～200000.
Component C.2 poly terephthalic acid alkane diol ester is the reaction product of aromatic dicarboxylic acid or its reactive derivative such as dimethyl ester or acid anhydrides and aliphatic series, cyclic aliphatic or araliphatic glycol, and even the mixture of this class reaction product.
Preferred poly terephthalic acid alkane diol ester comprises, with respect to dicarboxylic acid component 80wt% at least, and preferred 90wt% terephthalic acid residue at least, and with respect to diol component 80wt% at least, preferred 90wt% ethylene glycol and/or 1 at least, 4-butyleneglycol residue.
Except the terephthalic acid residue, preferred poly terephthalic acid alkane diol ester can comprise the highest 20mol%, the highest preferred 10mol%8～other aromatics of 14 carbon atoms or residue of cycloaliphatic dicarboxylic acid or 4～12 carbon atom aliphatic dicarboxylic acids, for example phthalic acid, m-phthalic acid, 2,6-naphthalene dicarboxylic acids, 4, the residue of 4 '-diphenyl dicarboxylic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, cyclohexanediacetic etc.
Except ethylene glycol or 1, outside the 4-butyleneglycol residue, preferred poly terephthalic acid alkane diol ester also can comprise the highest 20mol%, aliphatic diol or the cycloaliphatic diol of 6～21 carbon atoms, for example residue of following alcohol of preferred other 3～12 carbon atoms of the highest 10mol%: 1, ammediol, 2-ethyl-1, ammediol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanedimethanol, 3-ethyl-2, the 4-pentane diol, 2-methyl-2, the 4-pentane diol, 2,2,4-trimethylammonium-1, the 3-pentane diol, 2-ethyl-1, the 3-hexylene glycol, 2,2-diethyl-1, ammediol, 2, the 5-hexylene glycol, 1,4-two (β-hydroxy ethoxy) benzene, 2, two (4-hydroxy-cyclohexyl) propane of 2-, 2,4-dihydroxyl-1,1,3,3-tetramethyl-ring butane, 2, two (the 4-beta-hydroxy ethoxyl phenenyl) propane and 2 of 2-, (DE-OS 2 407 674 for propane for 2-two (4-hydroxyl propoxy-phenyl), 2 407776,2 715 932).
This poly terephthalic acid alkane diol ester can be more a small amount of three by adding-or tetrahydroxy alcohol or three-or the quaternary carboxylic acid reach branching, for example according to the method for DE-OS 1 900 270 and US-PS 3 692 744.Other preferred branching agents are 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, trimethylolethane and TriMethylolPropane(TMP) and tetramethylolmethane.
Especially preferred poly terephthalic acid alkane diol ester be those only by terephthalic acid and reactive derivative (for example, its dialkyl) thereof and ethylene glycol and/or 1, the preparation of 4-butyleneglycol, and the mixture of this type of poly terephthalic acid alkane diol ester.
The mixture of poly terephthalic acid alkane diol ester comprises 1～50wt%, preferred 1～30wt% polyethylene terephthalate and 50～99wt%, preferred 70～99wt% polybutylene terephthalate.
The limiting viscosity of the preferred poly terephthalic acid alkane diol ester that uses is generally between 0.4～1.5dl/g, and preferred 0.5～1.2dl/g measures in 25 ℃ of phenol/orthodichlorobenzenes (1: 1 weight ratio) with Ubbelohde viscometer.
The poly terephthalic acid alkane diol ester can adopt known method preparation (for example referring to " plastics handbook volume VIII, pp.695 rises, Carl Hanser press, Munich 1973).
Component D
The component D phosphonitrile that the present invention uses is the line style phosphonitrile of general formula (Ia) and the cyclic phosphazene of general formula (Ib)
Figure C9980793100151
Wherein the implication of R and k is with top identical.
Can enumerate following example: propoxy-phosphonitrile, phenoxy phosphazene, methylphenoxy phosphonitrile, amino phosphonitrile and fluoro-alkyl phosphonitrile.
Phenoxy phosphazene is preferred.
Phosphonitrile can use individually or with form of mixtures.General formula (Ia) can be always identical with residue R in (Ib), and perhaps 2 or a plurality of residue can differ from one another.
Phosphonitrile and preparation thereof are described in, for example among EP-A 728 811, DE-A 1 961 668 and the WO97/40092.
Component E
Component E comprises ultra-fine dispersive inorganic powder.
The ultra-fine dispersive inorganic powder E that the present invention uses preferably is made up of at least a kind of such polar compound: this compound is by the metal of a kind or multiple periodictable main group 1～5 or subgroup 1～8, preferably by main group 2～5 or subgroup 4～8, especially preferably by the metal of main group 3～5 or subgroup 4～8, with at least a kind be selected from the elementary composition of oxygen, hydrogen, sulphur, phosphorus, boron, carbon, nitrogen or silicon.
Preferred compound for example is oxide compound, oxyhydroxide, hydrous oxide, vitriol, sulphite, sulfide, carbonate, carbide, nitrate, nitrite, nitride, borate, silicate, phosphoric acid salt, hydride, phosphite or phosphonate.
Ultra-fine dispersive inorganic powder preferably is made up of oxide compound, phosphoric acid salt, oxyhydroxide, preferably by titanium dioxide, silicon-dioxide, tindioxide, zinc oxide, zinc sulphide, boehmite, zirconium dioxide, aluminum oxide, aluminum phosphate, ferric oxide, and even TiN, wolfram varbide, AlO (OH), antimonous oxide, ferric oxide, sodium sulfate, vanadium oxide, zinc borate, silicate such as pure aluminium silicate, Magnesium Silicate q-agent, 1-, 2-or 3-dimension silicate are formed.Mixture and doped compound also can use.
The also available organic molecule of these nano-scale particles carries out surface modification, with reach with composition in the compatible better purpose of polymkeric substance.Can obtain hydrophobic or hydrophilic surface in this way.
Hydrated aluminum oxide is boehmite or titanium dioxide for example, is especially preferred.
The average particulate diameter of this nano particle is less than or equal to 200nm, preferably is less than or equal to 150nm, especially 1～100nm.
Granularity and particle diameter always are meant average particulate diameter d 50, adopt super centrifugal according to the method mensuration of people such as W.Scholtan in " colloid and polymkeric substance magazine " 250 (1972), 782～796.
The add-on of this inorganic powder in thermoplastic composition, with the thermoplastic material be benchmark between 0.5～40, preferred 1～25, especially preferred 2～15wt%.
This mineral compound can be taked forms such as powder, thickener, colloidal sol, dispersion or suspensoid.Powder can be obtained through precipitation by dispersion, colloidal sol or suspensoid.
Powder is attached to adopts traditional method to implement in the thermoplastic composition, for example moulding compound and ultra-fine dispersion inorganic powder are directly mediated or extrusion molding.Preferable methods comprises makes masterbatch, for example in the component of flame-retardant additive and at least a kind of moulding compound of the present invention in monomer or solvent, or thermoplastic component and ultra-fine dispersive inorganic powder carry out co-precipitation, for example, randomly take the form of dispersion, suspensoid, thickener or the colloidal sol of this ultra-fine dispersion inorganic materials by the co-precipitation of water miscible liquid and ultra-fine dispersion inorganic powder.
Component F
Fluorinated polyolefin F is a high-molecular weight, and its second-order transition temperature is higher than-30 ℃, and usually above 100 ℃, fluorine content is preferably between 65～76,70～76wt% especially, average particulate diameter d 50Between 0.05～1000, preferred 0.08～20 μ m.The density of fluorinated polyolefin F is usually between 1.2～2.3g/cm 3Preferred fluorinated polyolefin F is multipolymers such as tetrafluoroethylene, poly(vinylidene fluoride), tetrafluoroethylene/hexafluoropropylene and ethylene/tetrafluoroethylene.Fluorinated polyolefin be known (referring to, " vinyl and related polymer ", Schildknecht work, JohnWiley ﹠amp; Sons company, New York, 1962, pp.484～494; " fluoropolymer ", Wall work, Wiley-international scientific company, John Wiley ﹠amp; Sons company, New York, volume 13,1970, pp.623～654; " contemporary plastics complete works ", 1970～1971, volume 47, no.10 A, in October, 1970, mcgraw-hill, inc, New York, pp.134 and 774; " contemporary plastics complete works ", 1975-1976, in October, 1975, volume 52, no.10A, McGraw-Hil company, New York, pp.27,28 and 472; And US-PS 3 671 487,3 723 373 and 3 838 092).
They can adopt currently known methods preparation, for example by tetrafluoroethylene in water medium, generate in the presence of catalyzer such as Sodium persulfate, potassium or the ammonium at free radical, 7～71kg/cm 2Pressure and 0～200 ℃ temperature, preferred 20～100 ℃ temperature is carried out polymerization (further details is for example referring to, United States Patent (USP) 2 393 967).Decide on the form that they use, the density of these materials can be between 1.2～2.3g/cm 3, mean particle size is between 0.5～1000 μ m.
Preferred fluorinated polyolefine F of the present invention is a tetrafluoro ethylene polymer, average particulate diameter 0.05～20 μ m, preferred 0.08～10 μ m, density 1.2～1.9g/cm 3, and preferably use with the cohesion mixture form of tetrafluoro ethylene polymer F emulsion and graftomer B emulsion.
The suitable fluorinated polyolefin F that can powder type uses is that average particulate diameter 100～1000 μ m, density are between 2.0g/cm 3～2.3g/cm 3Tetrafluoro ethylene polymer.
The preparation of the cohesion mixture of B and F is at first the water miscible liquid (latex) of graftomer B to be mixed with the emulsion of the tetrafluoro ethylene polymer F of fine dispersion; The solids content of suitable tetrafluoro ethylene polymer emulsion is usually between 30～70wt%, 50～60wt% especially, preferred 30～35wt%.
Consumption about B component described herein can comprise the ratio by graftomer in the cohesion mixture of graftomer and fluorinated polyolefin preparation.
Graftomer B and the weight ratio of tetrafluoro ethylene polymer F in emulsion mixture are 95: 5～60: 40.Emulsion mixture is condensed by currently known methods subsequently, for example by spraying drying, lyophilize or by adding inorganic or organic salt, acid, alkali or organic water-miscible solvent such as alcohols, ketone is realized cohesion, preferably at 20～150 ℃, and 50～100 ℃ temperature especially.Need, can be at 50～200 ℃, preferred 70～100 ℃ are carried out drying.
Suitable tetrafluoro ethylene polymer emulsion is traditional commercially available prod, for example presses trade(brand)name Teflon by E.I.Du Pont Company 30 N sell.
Moulding compound of the present invention can comprise at least a kind of conventional additive, for example lubricant and releasing agent, nucleator, static inhibitor, stablizer and dyestuff and pigment.
Moulding compound of the present invention can comprise, and with respect to total moulding compound, the highest 35wt% another kind is the synergic fire retardant randomly.The example of the another kind of fire retardant that can enumerate is an organo phosphorous compounds, for example is described in EP-A 363 608, EP-A 345 522 and EP-A 640 655; Organohalogen compounds, for example decabromodiphynly oxide, tetrabromobisphenol, inorganic halides such as brometo de amonio, nitrogen compound such as melamine, melamine/formaldehyde resin, inorganic hydroxide such as magnesium hydroxide, aluminium hydroxide, mineral compound such as weisspiessglanz, barium metaborate, hydroxoantimonate (hydroxyl coordination metaantimmonic acid), zirconium white, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate, ammonium borate, barium metaborate, talcum powder, silicate, silicon-dioxide and stannic oxide, and silicone compounds.
Moulding compound of the present invention, wherein comprise component A～F and randomly other additives known such as stablizer, dyestuff, pigment, lubricant and releasing agent, nucleator and static inhibitor person, can press known way by these concrete components mixes, and be placed in conventional apparatus such as Banbury mixer, forcing machine and the twin screw extruder them at 200 ℃～300 ℃ temperature melting mixing and extrude preparation, wherein component F preferably uses with above-mentioned cohesion mixture form.
Each component can be taked the mode of order or adding simultaneously by the mixing of known way and can carry out in about 20 ℃ (room temperatures) or at comparatively high temps.
Rely on its excellent anti-flaming performance and heat-resisting, and such as the premium properties of weld line strength and ESC behavior aspects such as (proof stress be full of cracks), thermoplastic composition of the present invention is applicable to production all kinds mo(u)lded item, those of the resistance to fracture of especially having relatively high expectations.
Moulding compound of the present invention can be used for producing any kind of mo(u)lded item.This mo(u)lded item especially can adopt injection moulding production.Producible mo(u)lded item example is: various shells, and household electrical appliance for example are as fruit juice extractor, coffee-maker, food mixing machine; Be used for office equipment, for example indicating meter, printer, duplicating machine; Perhaps building trade and auto parts clad steel plate.They also can be used for the electric works field, because they have extraordinary electric property.
Have, moulding compound of the present invention also can be used to produce for example with lower molding and molded article again:
The electric appliance casing of rail vehicle interior finish, wheel hub lid, interior dress small transformers, information propagation and sending spparatus shell, medical shell and coating layer, massaging appts and shell thereof, children toy car, wallboard key element, safety equipment shell, hatchback (automobile) interceptor, heat insulation transportation trough tank, animalcule stable breeding equipment, health and bath equipment mo(u)lded item, ventilation opening grid, summer home and shed mo(u)lded item, gardening equipment shell.
Another kind of working method is to produce mo(u)lded item by the sheet material of former production or film are carried out thermoforming.
Therefore, the present invention also provides moulding compound of the present invention producing various mo(u)lded items, the application of preferred those aspects above-mentioned, and the mo(u)lded item of being made by moulding compound of the present invention.
Embodiment
Component A
Linear bisphenol A base polycarbonate, its relative solution viscosity are 1.252, its medium viscosity system according to the solution form of 0.5g/100mL in methylene chloride 25 ℃ of mensuration.
B component
Graftomer comprises 40 parts by weight of styrene and the vinyl cyanide multipolymer in 73: 27 ratio preparation, is grafted to granular, crosslinked polybutadiene rubber (the average particulate diameter d of 60 weight part emulsion polymerization prepared 50=0.28 μ m) on.
Component C
Styrene/acrylonitrile copolymer comprises styrene/acrylonitrile, by weight 72: 28, and limiting viscosity 0.55dl/g (20 ℃, in dimethyl formamide, measure).
Component D
The phenoxy phosphazene that general formula is following
Figure C9980793100191
Commercially available product P-3800, Nippon Soda company (Japan) makes.
Component E
Pural 200, a kind of hydroxide aluminum oxide (Condea company (hamburger, Germany) provides), the about 50nm of mean particle size.
Component F
The cohesion mixture form of tetrafluoro ethylene polymer is made by SAN graftomer water miscible liquid and a kind of tetrafluoro ethylene polymer water miscible liquid corresponding to said components B.The weight ratio of graftomer B and tetrafluoro ethylene polymer F is 90wt% in this mixture: 10wt%.The solids content of tetrafluoro ethylene polymer emulsion is 60wt%; Average particulate diameter is between 0.05～0.5 μ m.The solids content of SAN graftomer emulsion is 34wt%; Average latex particle diameter d 50=0.28 μ m.
The preparation of F
The emulsion of tetrafluoro ethylene polymer (Teflon 30N, E.I.Du Pont Company provides) is mixed with the emulsion of SAN graftomer B, and carries out stabilization with the 1.8wt% phenolic antioxidant with respect to polymer solids.At 85～95 ℃, mixture utilizes the pH that acts on of sal epsom (Epsom salt) aqueous solution and acetate to equal 4～5 and condense, and filters also washing in fact not containing ionogen, then, shifts out most of water by centrifugal, and material is dried to powder at 100 ℃ then.This powder can carry out mixing in described device with other components.
The preparation of moulding compound of the present invention and test
All components are mixed in the 3L Banbury mixer.In Arburg 270E type injection moulding machine, make mo(u)lded item for 260 ℃.
Sample strip to size 80 * 10 * 4mm is measured dimension card B softening temperature according to DIN 53 460 (ISO 306).
Measure notched Izod impact strength a according to ISO 180/1 A k
The measuring method of weld line strength is: according to DIN 53 453 measure from two sides injection moulding (260 ℃ of processing temperatures) form, the sample of size 170 * 10 * 4mm is in the shock strength of welded bonds.
The fire resistance of sample is according to UL-Subj.94 V, on injection moulding machine, sample bar 260 ℃ of preparations, size 127 * 12.7 * 1.6mm carries out.
The implementation procedure of UL 94 V test is as follows:
Material sample is configured as the strip of 127 * 12.7 * 1.6mm.The sample bar is vertically fixing, makes this sample bar base in each case be positioned at 305mm place, meche (dressing) top.Each sample bar continues 10s by 2 ignition operation in succession at every turn, lights separately, observes the combustion characteristic after at every turn lighting, and then sample is made assessment.Sample is lighted with Bunsen burner, and its Sweet natural gas blue flame height is 100mm (3.8 inches), and thermal content is 3.73 * 10 4KJ/m 3(1000 BTU/ cubic feet).
UL 94 V-0 grades comprise that material is measured according to UL 94 V methods and shown character as described below.The moulding compound of this one-level comprises, be exposed to test flame at every turn after the none sample combustion surpass 10s; Each sample sets all is being no more than 50s through sum combustion time that they show after being exposed to for 2 times altogether; The none sample is burnt fully up to the clip place that is clipped in the sample upper end in the middle of them; The none sample lights the cotton hair that is arranged in below the sample by its burning drop or particle in them; In them also the none sample continue to glow behind the flame removing test above 30s.
Other UL 94 grades show, because they can discharge drop or the particle of lighting, so anti-flaming or the self-extinguishing energy is relatively poor.These grades are respectively UL 94 V-1 and V-2." defective " is the sample grade that is equal to or greater than 30s combustion time.
Proof stress be full of cracks behavior (ESC behavior) is to carry out at the sample strip of 260 ℃ of size 80 * 10 * 4mm, processing temperature.The test(ing) medium that uses is the mixture of 60% (volume) toluene and 40% (volume) Virahol.Sample is attached to earlier on the circular arc pattern to be accepted thick stress and handles that (initial elongation %), is immersed in the test(ing) medium of room temperature then.According to be full of cracks or destructive situation in test(ing) medium, occur with the increase of initial elongation, assess the stress crack behavior.
Following table 1 has been summed up the performance of moulding compound of the present invention:
By being used in combination of phosphonitrile and ultra-fine dispersion inorganic powder, the moulding compound thermotolerance that is obtained is improved, and it is characterized in that, has such as mechanical propertys such as splendid notched Izod impact strength, proof stress be full of cracks and weld line strengths splendid.Surprisingly, the good anti-flaming property of moulding compound of the present invention is to obtain under the situation that adopts obvious lesser amt phosphonitrile.
Table: moulding compound and performance thereof
1 (Comparative Examples) 23
Component [weight part]
A 66.7 66.7 66.7
B 7.3 7.3 7.3
C 9.4 9.4 9.4
D 15.0 13.0 11.0
E - 1,0 1,0
F 4.2 4.2 4.2
Character
a k[kJ/m 2] 56 58 59
B120[℃ on dimension card] 101 104 110
a n(welded bonds) [kJ/m 2] 15.8 17.8 17.8
The ESC-behavior,
Destroy, at [%] 1.6 1.8 2.0
UL94V1,6mm V-0 V-0 V-0

Claims (20)

1. thermoplastic composition comprises:
A) at least a in 40～99 weight part aromatic polycarbonates and the polyestercarbonate,
B) 0.5～60 weight part graftomer, it contains
B.1) one or more vinyl monomers of 5～95wt% and
B.2) one or more grafting main chains of 95～5wt%, the second-order transition temperature of this main chain are less than 10 ℃,
C) at least a thermoplastic polymer of 0～45 weight part is selected from least a in vinyl (being total to) polymkeric substance and the poly terephthalic acid alkane diol ester,
D) at least a component that is selected from the phosphonitrile of general formula I a and Ib representative of 0.1～50 weight part
Figure C9980793100021
Wherein
Every kind of situation of R can be identical or different, and representative (i) is selected from amino and C 1～C 8At least a in the alkyl, optional by halogenation with (ii) be selected from C under every kind of situation 1～C 8Alkoxyl group, C 5～C 6Cycloalkyl, C 6～C 20Aryl and C 7～C 12At least a in the aralkyl, under every kind of situation randomly by at least a replacement in alkyl and the halogen,
K represents 0 or 1～15 number,
E) 0.5～40 weight part fine dispersion inorganic powder, its average particulate diameter is less than or equal to 200nm,
This component E) is selected from: titanium dioxide, silicon-dioxide, tindioxide, zinc oxide, zinc sulphide, boehmite, zirconium dioxide, aluminum oxide, aluminum phosphate, ferric oxide, TiN, wolfram varbide, AlO (OH), antimonous oxide, ferric oxide, sodium sulfate, vanadium oxide, zinc borate, pure aluminium silicate and Magnesium Silicate q-agent.
And
F) 0～5 weight part fluorinated polyolefin.
2. the moulding compound of claim 1 comprises
60～98.5 weight part A,
1～40 weight part B,
0～30 weight part C,
2～35 weight part D,
1～25 weight part E,
0.15～1 weight part F.
3. the moulding compound of claim 1 comprises 2～25 weight part C.
4. the moulding compound of claim 1 comprises 5～25 weight part D.
5. the moulding compound of claim 1, therein ethylene base monomers B .1 are the mixtures by following component preparation:
B.1.1 50～99 parts by weight of ethylene base aromatic hydrocarbons and/or nuclear substituted vinyl-arene and/or methacrylic acid C 1～C 8Alkyl ester, and
B.1.2 1～50 parts by weight of ethylene base prussiate and/or (methyl) vinylformic acid C 1～C 8-alkyl ester and/or olefinically unsaturated carboxylic acid derivatives.
6. the moulding compound of claim 1, wherein the grafting main chain is selected from least a rubber in elastoprene, EP (D) M rubber, acrylic elastomer, urethanes, silicone rubber, neoprene and the ethylene/vinyl acetate rubber.
7. the moulding compound of claim 1, wherein component D is selected from propoxy-phosphonitrile, phenoxy phosphazene, methylphenoxy phosphonitrile, amino phosphonitrile and fluoro-alkyl phosphonitrile.
8. the moulding compound of claim 1, wherein component E is selected from least a polar compound, by the metal of one or more periodictable main groups 1～5 or subgroup 1～8 and at least aly be selected from the elementary composition of oxygen, hydrogen, sulphur, phosphorus, boron, carbon, nitrogen or silicon.
9. the moulding compound of claim 8, wherein component E is selected from least a polar compound, by the metal of one or more periodictable main groups 2～5 or subgroup 4～8 and at least aly be selected from the elementary composition of oxygen, hydrogen, sulphur, phosphorus, boron, carbon, nitrogen or silicon.
10. the moulding compound of claim 9, wherein component E is selected from least a polar compound, by the metal of one or more periodictable main groups 3～5 or subgroup 4～8 and at least aly be selected from the elementary composition of oxygen, hydrogen, sulphur, phosphorus, boron, carbon, nitrogen or silicon.
11. the moulding compound of claim 1, wherein component E is selected from least a in oxide compound, oxyhydroxide, hydrous oxide, vitriol, sulphite, sulfide, carbonate, carbide, nitrate, nitrite, nitride, borate, silicate, phosphoric acid salt, hydride, phosphite and the phosphonate.
12. the moulding compound of claim 1, wherein component E is selected from oxide compound, phosphoric acid salt and oxyhydroxide.
13. the moulding compound of claim 1, wherein component E is selected from: 1-, 2-or 3-dimension silicate.
14. the moulding compound of claim 1, wherein component E is selected from hydrated aluminum oxide, titanium dioxide and composition thereof.
15. the moulding compound of claim 1 comprises at least a additive, is selected from lubricant and releasing agent, nucleator, static inhibitor, stablizer, dyestuff and pigment.
16. the moulding compound of claim 1 also comprises the fire retardant that is different from component D.
17. the method for the moulding compound of production claim 1, wherein component A～E and randomly further additive mix and melting mixing together.
18. the moulding compound of claim 1 is used to produce the application of mo(u)lded item.
19. the mo(u)lded item of producing by the moulding compound of claim 1～16.
20. the casing part of claim 19.
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